Med Chem Res
5
C , C ), 212.07 s (C ), 15.89 q, 16.28 q (C , C ), 121.35 d
7
6
11 12
1
11
H NMR (CDCl ): 0.80 s (3H) and 0.82 s (3H) (C H ,
(
(
(
(
3
3
13
14
15
16
C ), 141.95 s (C ), 32.50 t (C ), 26.11 t (C ), 124.07 d
12
18
19
C H ), 0.83 s (3H, C H ), 1.24 s (3H, C H ), 1.63 ddd
3 3 3
1
7
18
19
20
C ), 131.62 s (C ), 25.56 q (C ), 23.39 q (C ), 17.40 q
2
(1H, J = 13.8, J
13
13
= 9.2, J13,2 = 6.5, H ), 1.79–
21
1
3,14
17
0
21
C ).
1.94 m (3H, H , 2H ), 1.97 s (3H, C H ), 1.98–2.07 m
3
1
1H, H ), 2.69 br d (2H, J = 13.7), 3.02 dd (1H,
4
2
(
1
Z-isomer H NMR (CDCl ): 0.84 s (3H) and 0.88 s (3H)
2
4
2
4
J = 13.1, J = 3.2), 3.03 dd (1H, J = 13.1, J = 3.2),
3
1
1
12
C H , C H ), 1.59 br s (3H, C H ), 1.66 m (3H, all
21
2
3.19 dd (1H, J = 13.1, J = 3.2), 3.21 dd (1H, J = 13.1,
4
2
(
3
3
3
1
J B 2.5, C H ), 1.72 br s (C H ), 2.04–2.09 m (2H, H ),
1
.10–2.14 m (2H, H ), 2.73–2.77 m (2H), 3.07–3.11 m
9
20
15
4
2
J = 3.2), 3.33 dm (1H, J = 13.7, others J \ 4.0),
3.36 dm (1H, J = 13.7, others J \ 4.0)—4NCH , 2.76 dd
3
3
6
2
2
2
1
6
= 7.4, H ), 3.74 dd (1H,
(
2H), 3.31–3.36 m (2H), 3.45–3.51 m (2H)—4NCH , 4.61
2
(1H, J16;170 ¼ 10:3, J
16,17
2
br d (1H, J2,13 = 5.5, H ), 5.08 tqq. (1H, J
2
13
= 7.0,
13
J2;130 ¼ 7:7, J
= 6.5, H ). C NMR (CDCl ): 76.26 d
2,13 3
17,16
1
7
2
(C ), 58.40 t, 58.67 t, 67.60 t, 67.61 t (C , C , C , C ),
4
8
9
10
J
1
= J17,21 = 1.4, H ), 5.48 dm (1H, J = 5.5, H ).
13,2
1
3
7,19
2
C NMR (CDCl ): 75.55 d (C ), 59.74 t, 59.77 t, 67.13 t,
5
45.48 s and 45.70 s (C , C ), 211.44 s (C ), 15.62 q and
7
6
3
4
8
9
10
5
7
7.19 t (C , C , C , C ), 45.21 s, 45.93 s (C , C ), 212.
11
16.20 q (C , C ), 30.27 t (C ), 38.63 d (C ), 42.96 s
12
13
14
6
0
6
5
6
11
12
13
3 s (C ), 15.89 q, 16.31 q (C , C ), 120.68 d (C ), 141.
15
16
17
18
(C ), 54.08 d (C ), 22.98 t (C ), 17.14 q (C ). 30.07 q
1
4
15
16
17
0 s (C ), 39.68 t (C ), 26.27 t (C ), 124.88 d (C ), 131.
19
(C ), 207.51 s (C ), 29.88 q (C ). HRMS: 318.2307
20
21
1
8
19
5 s (C ), 25.60 q (C ), 16.81 q (C ), 17.59 q (C ).
20
21
?
?
(M , C H N O ; calc. 318.2302).
19 32 2 2
?
?
HRMS: 302.2351 (M , C H N O ; calc. 302.2353).
19 30 2
2
-(2,6-Dimethylhept-5-en-1-yl)-5,7-dimethyl-1,3-
5,7-Dimethyl-2-(((1R)-2,2,3-trimethylcyclopent-3-en-1-
diazaadamantan-6-one (5f)
yl)methyl)-1,3-diazaadamantan-6-one (5h)
The reaction of bispidinone 4 (0.061 g (0.37 mmol)) and
aldehyde 6f (0.057 g (0.37 mmol)) for 10 min gave rise to
compound 5f (0.059 g, 54 %).
The reaction of bispidinone dihydrochloride 4Á2HCl
(
(
0.087 g (0.36 mmol)), 0.093 g Et N and aldehyde 6h
3
0.054 g (0.36 mmol)) for 15 min gave rise to compound
5.5
1
11
2
1
H NMR (CDCl ): 0.84 s (3H) and 0.87 s (3H) (C H ,
3
3
5h (0.068 g, 63 %). [a]D = 7 (c = 1.2, MeOH).
H
1
C H ), 0.94 d (3H, J
2
20
= 6.6, C H ), 1.21 dddd (1H,
1
3
20,14
3
NMR spectrum of compound 5h coincided with H NMR
spectrum of 5i.
2
15
= 7.6, J15;160 ¼ 6:0, H ),
J = 13.5, J15,16 = 9.8, J
15,14
2
1
.38 dddd (1H,
5
J = 13.5, J150;160 ¼ 9:8; J150;14 ¼
0
1
2
J1
0
¼ 5:8; H ), 1.49 ddd (1H, J = 13.7, J
= 8.6,
5 ;16
13,14
1
J1 = 5.9, H ), 1.59 br s (3H, C H ), 1.53–1.63 m (1H,
3
21
3,2
3
5,7-Dimethyl-2-(((1S)-2,2,3-trimethylcyclopent-3-en-1-
1
4
19
H ), 1.66 m (3H, all J B 2.5, C H ), 1.92 ddd (1H,
yl)methyl)-1,3-diazaadamantan-6-one (5i)
3
0
13
2
J = 13.7, J
0
¼ 8:1; J
0
13 ;14
¼ 5:2; H ), 1.90–2.08 m
1
3 ;2
1
2H, 2H ), 2.73 dd (1H, J = 13.7, J = 3.0), 2.74 dd (1H,
6
2
4
(
2
The reaction of bispidinone dihydrochloride 4Á2HCl
4
J = 13.7, J = 3.0), 3.07–3.12 m (2H), 3.27 dd (1H,
(0.06 g (0.25 mmol)), 0.065 g Et N and aldehyde 6i
3
2
4
J = 13.0, J = 3.3), 3.29 dd (1H, J = 13.0, J = 3.3),
2
4
(0.037 g (0.24 mmol)) for 15 min gave rise to compound
27.5
5i (0.045 g, 62 %). [a]D = -14 (c = 0.1, MeOH).
2
.39 dd (1H, J = 13.7, J = 3.3), 3.44 dd (1H, J = 13.7,
4
2
3
4
1
20
J = 3.3)—4NCH , 3.93 dd (1H, J2;130 ¼ 8:1, J
= 5.9,
17
= 1.5, H ).
H NMR (CDCl ): 0.77 s (3H, C H ), 0.84 s (3H) and
3 3
2
2,13
2
H ), 5.09 tqq (1H, J
11
12
19
= 7.0, J
= J
0.86 s (3H) (C H , C H ), 0.97 s (3H, C H ), 1.57 m
3 3 3
1
7,16
17,19
17,21
1
3
2
C NMR (CDCl ): 76.14 d (C ), 58.74 t, 59.00 t, 67.93 t,
21
13
3
(3H, all J B 3.0, C H ), 1.56–1.62 m (1H, H ), 1.83–
3
2
1.92 m (2H, H , H ), 2.11 ddd (1H, J = 13.8,
4
7.96 t (C , C , C , C ), 45.63 s, 45.86 s (C , C ),
8
9
10
5
7
14
18
6
2
2
1
6
11.81 s, (C ), 15.78 q, 16.36 q (C , C ), 37.28 t (C ),
11
12
13
130
180
J1
3 ;2
0
¼ 9:3; J
13 ;14
0
¼ 2:9; H ), 2.25–2.33 m (1H, H ),
1
4
15
16
17
9.71 d (C ), 37.13 t (C ), 25.33 t (C ), 124.63 d (C ),
2
4 2
2.72 dd (1H, J = 13.6, J = 3.0), 2.75 dd (1H, J = 13.6,
1
31.09 s (C ), 25.59 q (C ), 19.41 q (C ), 17.57 q (C ).
8
19
20
21
4
2
J = 3.0), 3.07 dd (1H, J = 13.2, J = 3.0), 3.08 dd (1H,
4
?
?
2
4
J = 13.2, J = 3.0,), 3.24 dd (1H, J = 13.2, J = 3.3),
2
4
HRMS: 304.2511 (M , C H N O ; calc. 304.2509).
19 32 2
2
4
2
.28 dd (1H, J = 13.2, J = 3.3), 3.37 dd (1H, J = 13.6,
3
4
2
4
2
-(((1R,3R)-3-Acetyl-2,2-dimethylcyclobutyl)methyl)-5,7-
J = 3.3), 3.48 dd (1H, J = 13.6, J = 3.3)—4CNH ,
2
2
dimethyl-1,3-diazaadamantan-6-one (5g)
3.88 dd (1H, J
0
¼ 9:3, J
= 4.8, H ), 5.19 m (1H, all
2,13
2
13
;13
1
J B 4.0, H ). C NMR (CDCl ): 77.04 d (C ), 58.47 t,
7
2
3
4
8
9
10
58.94 t, 67.80 t, 67.88 t (C , C , C , C ), 45.63 s, 45.84 s
The reaction of bispidinone 4 (0.061 g (0.37 mmol)) and
aldehyde 6g (0.06 g (0.36 mmol)) for 15 min gave rise to
5
(C , C ), 211.71 s (C ), 15.71 q, 16.32 q (C , C ), 30.35 t
7
6
11
12
2
5.5
13
(C ), 46.71 d (C ), 46.49 s (C ), 148.23 s (C ), 121.49
14
15
16
compound 5g (0.088 g, 77 %). [a]D = -27 (c = 1.6,
MeOH).
1
7
18
d (C ), 35.15 t (C ), 25.46 q (C ), 19.60 q (C ), 12.43 q
19
20
1
23